Derivatives of dioxydiamino-arsenobenzene and process of making same.



UNITED srnrrns .PnrE T OFFICE.

FRIEDRICH STOLZ AND FRANZ FLACHER, F HOCHST-ON-THE-MA'IN, GERMANY, AS-

SIGNORS TO FARBWERKE VORM. MEISTER LUCIUS & BRlllNING, THE-MAIN,GERMANY, A CORPORATION OF GERMANY.

or Keener-01w DERIVATIVES OF DIOXYDIAMINO-ARSEN'OBENZENE AND'PROGESS OFMAKING SAME.

No Drawing.

To all whom it may concern:

Be" it known that we, FRIEDRICH S'roLz,

'- Ph. D., chemist, andl RANz FLACHER, Ph.

D., chemist, citizens of the Empire of Germany, residing atHiichst-on-the-llain, Germany, have invented certain new and usefulImprovements in Derivatives of Dioxydiamino-Arsenobenzene and Processesof Making Same, of which the following is a specification. I

We have found that new acids of great value can be obtained by causingmonohalok gen-acetic acid or a homologue thereof to vantages as comparedwith the form in' which the d1oxydianunoarsenobenzene has.

been used hitherto, namely-an acid solution or an alkaline solution oraneutral suspenslon, because the use 'of the said salts in therapeuticsis not attended by undesirable secondary eifects- These new productscontainthe radical:

I wherein the X stands for theresidue of a fatty acid.

The following examples illustrate the in- Vention: 1

Example I: A solution of 100 grams of dioxydiaminoarsenobenzenedihydrochlorid in 300 com. each of inethylal'cohol and water isneutralized with, caustic soda lye. There is then added to thesuspension of the tree base thus obtained a solution of 4.0 grams ofchloracetic-acid in 5 to 10 times its weight of water and the whole isheated for some hours 30-60-65 CI, advantageously with exclusionof air,which can be attained by introducing an indifferent gas such as carbon Idioxid, hydrogen ornitrogen; during the heating the suspended basedissolves. The dioxyaminoarsenobenzene-a1nino-acetic acid thus formed iscaused to se arate by adding caustic soda lye until the iquid no longershows any but a feebly acid reaction, it is Specification of LettersPatent. Patented Dec. 24,1912. Application filed March 16,1912. Serial110,684,303. I

then filtered oil and washed with water.. If potassium iodid be presentduring the reaction of the ehloracetic acid, the transforma-- tion isgreatly facilitated. In the place of'a solution: of free chloraceticacid there may be employed a solution of the sodium salt of chloraeeticacid; in this case the product remains undissolved. If an excessofhal'ogen-acetic acid, for instance 4% molecular proportions of it, iscaused to act upon dioxydiaminoarsenobenzene, or if the dioxyaminoarsenobenzene-monoamino-acetic acid is again treated withhalogenacetic acid,.the-

dioxyarsenobenzene-diamino-acetic acid is;

obtained.

Example II: 100 gr am s of hydrochlorid m I of dioxydiaminoarsenobenzeneare dissolved in 300 ccm. of methyl alcohol andiSOO com.

of water and mixed with l molecular proportions of caustic soda lye.'The clear solus tion is mixed with a solution of 50 grams of sodiumchloracetate and 36 grains of potassi'u'm iodid in 510 times theirweight of water and heated for three hours to GO-65 C. without access ofair. The product thus formed is separated by slightly acidifying thealkaline solution, and is then further treated as indicated in ExampleI.. The

dioxyaminoarsenobenzene-amino-acetic v on Nncmcoos forinsa yellowpowder, readily soluble in alkalis and in an excess of acid. It is insoluble in almost all of the usual so1vents.- For transforming the acidinto the sodiumsalt, it is mixed and stirred with water to ,form a thinmagma, to which causticsoda lyev or a solution of sodium carbonate isadded until the reaction is neutral; the solu- 7 tion thus obtained isfiltered and mixed with ten times its weight of-alcohol'or acetone.

The sodium salt thus precipitated is filtered and 'ashed with alcoholand ether. Instead of precipitating the aqueous solution of the sodiumsalt with alcohol or acetone, this solution may be evaporated in avacuum. The sodium salt of 'the dioxyaminoarsenobenzene-amino-aceticacid is of a yellowishbrown color; it readily dissolves to a neutralsolution water. It is insoluble in alcohol and acetone. By adding to theaqueous solution dilu'ted' hydrochloric acid, a yellow, flakyprecipitate is obtained which redissolves in an excess of acid. It forthe neuwhich, on addition of a small quantity of it to this.

ammonia, becomes again clear. solution diluted hydrochloric is added, ayellow, iialty precipitate separates which ire-dissolves in an excess ofacid.

Example Ill: One molecula proportion of dihydrochlorid of dioxydt.benzene is dissolved in three times its quantity of methyl alcohol andwater and nontralized with caustic soda lye. To the separated base areadded 2 molecular proportions of cz-brompropionic acid dissolved inthree to five times its quantity of water, and the mixture is heated to60435" C. until the separated base is dissolved. After cooling, causticsoda lye is gradually added so long as there is still. a teebly acidreaction; the dioxyami'noarsenohenzone alninopropionic acid thusisolated is filtered oil and washed with Water. Thedioxyaminoarsenobenzeneamino-propionic acid is of a yellow color, itdissolves in alkalis, and also in an excess of hydrochloric acid, and isinsoluble n almost all of the usual of alcohol or acetone.

solvents. For preparing the sodium salt of the dioxyaminoarsenobenzcneamino propionic acid, the acid is diluted with water so as to form athin magma, and neutralized with caustic soda lye or a solution ofsodium carbonate. The solution thus obtained is filtered and mixed withten times its Weight The sodium salt thus precipitated is filtered andwashed with alcohol. The sodium salt of thedioxyaniinoarsenobenzene-amino-pr0pionic acid is a yellow powder,readily dissolving to a neutral solution in water and being insoluble inalcohol and acetone. By adding to the aqueous solution hydrochloricacid, a yellow precipitate forms which re-dissolves in an excess ofacid.

Example IV: 500 grams of dihydrochlorid of dioxydiaminoarsenobenzene aredissolved in 1500 ccm. each of methyl alcohol and water and neutralizedwith caustic soda lyc. After having added 820 grams of bromacetic acidin 5 times its weight of water, the mixture is heated for one hour to65' 0., while introducing nitrogen,

is then precipitated by gradually adding caustic soda lye until theliquid shows but a feebly acid reaction. It is filtered under pressure,washed with water'and for transforming it into the di-sodium salt, isneutralized with caustic soda lye. This disodium salt is precipitatedfrom the filtered solution with alcohol or acetone. Thedioxyarsenobenzene-diainino-acetic acid may also be prepared by usingfrom the outset 4 instead of 2 molecular proportions of bromacetic acid.The separation of the dioxyaminoarsenobenzene-mono-amino acetic acidthereby becomes unnecessary. The disodium salt of thedioxyarsenoben'zenediamino-acetic acid is of a yellowish-brown color andreadily dissolves inwater with neutral reaction, being insoluble inalcohol and acetone. By adding to the aqueous solutiondilutedhydrochloric acid, a yellow",

flaky precipitate is obtained, which redissolves in an excess of acid.

Having now described our invention, what We claim, is:

l. The process of manufacturing derivatives ofdioxydiaminoarsenobenzene, which consists in causing themonohalogen-substituted'acids of the aceticacid series to act upondioxydiaminoarsenobenzene.

2. The process of manufacturing derivatives ofdioxydiaminoarscnobenzene, which consists in causing monohalogen-aoeticacid :to act upon dioxydiaminoarsenobenzene.

' 3. As new products, the glycin derivatives ofdioxydiaminoarsenobenzene con taining the radical:

wherein the X stands for the residue ofa fatty acid, said products beingyellow powders, readily soluble in alkalis and in an excess ofhydrochloric acid, insoluble in almost all of the organic solvents,forming in the shape of their alkali salts yellow to yellowish-brownpowders which readily dissolve in water with a neutral reaction 'and areinsoluble in alcohol and acetone.

4. As a new product, the derivative of dioXydiaminoarsenobenzene of theconstitution NHCHQCOOH said product being a yellow powder readilyFRIEDRICH sToLZ; FRANZ FLAOHER.

Witnesses:

JEAN GRUND, CARL GRUND. I

